Split-Ring Resonator Plasma Source
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of priority to U.S. Provisional Application No.
61/831,678, filed June 6, 2013, the entire contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a miniaturized plasma source, and in particular a split- ring resonator and a laser spectroscopy device comprising such.
BACKGROUND
[0003] Miniaturized plasma sources are used in a variety of applications, e.g., in chemical analysis, for sterilization or activation of different substances, or as ion sources. Some of their advantages are low power consumption, simple design and fabrication, mechanical robustness, long lifetime, high non-thermal plasma density, and the ability to operate at atmospheric pressure, although they also suffer from some limitations.
[0004] Miniaturized plasma sources based on microstrip split-ring resonators (MSRRs) have received an increasing amount of interest during the last decade. A microstrip is a radio frequency transmission line consisting of a dielectric substrate sandwiched between a metal strip and a metal ground plane, as shown in Figure 1(a). In the case of an MSRR, the metal strip is a dipole folded into a circle, with the two ends creating a small gap, as shown in Figure 1(b), over which an electric field can be created. Here, the dipole corresponds to a half-wavelength microwave resonator often used as an antenna. The dipole is connected to an additional microstrip transmission line, a feed line that supplies it with radio frequency (RF) power.
[0005] At resonance, the electric potential at the ends of the dipole is 180° out of phase, enabling the amplitude of the electric field between them to be amplified several orders of magnitude. Hence, with a relatively low input power, a large potential is created over the gap, and this potential is used to ignite and maintain a plasma, as shown in Figure 1(c). The large potential arises because when a standing wave is created in a dipole, the current is zero at the endpoints and at its maximum at the middle of the strip. Correspondingly, the electric potential is at its
maximum and minimum, respectively, at the endpoints, although the two ends are 180° out of phase, and zero at the middle.
[0006] The electric field in a microstrip is mostly confined to the dielectric substrate. However, in the gap of a split-ring resonator, the electric field between the ends of the folded dipole is elevated from the substrate and is concentrated in the plane between the two ends. This provides one of the key features of the MSRR, i.e., that most of the electric field is concentrated to the gap. It should be noted that no DC potential is applied to the plasma, minimizing energy lost to moving ions.
[0007] In order to effectively operate the MSRR, the input impedance of the ring should match the impedance of the feed line. The characteristic impedance of the ring depends on the offset of the feed line from the center of the dipole, and the quality factor of the microstrip.
[0008] One laser spectroscopy technique using a plasma source is optogalvanic spectroscopy (OGS) in general and intracavity optogalvanic spectroscopy (ICOGS) in particular. Both are based on the optogalvanic (OG) effect. Using this, the interaction of an incident laser beam with atoms or molecules present in a plasma induces changes in the electrical properties (e.g., voltage or impedance) of the plasma which can be measured electrically. The measured impedance change is proportional to the number of interacting molecules but will also depend on the plasma parameters, e.g., pressure, as well as the laser intensity and gas composition in the discharge.
[0009] By using an isotope-specific C02 laser as the source of the radiation, i.e. a laser with a wavelength identical to one of the isotope-specific transitions in the mid-IR spectrum of C02, it has been shown that OGS can be applicable to measurements of the isotopic composition of carbon-containing samples, e.g., the 13 C/ 12 C ratio, for, e.g., ulcer diagnostics, and that it might even be possible to measure the 14C/12C ratio using the ICOGS technique. The schematic of a standard ICOGS system is shown in Figure 2. As shown in Figure 2, a sample cell 10 is inserted into the laser cavity 14 of a laser 15, with a lasing frequency corresponding to a transition in the spectrum of the active laser medium 16 (which may be a moiety of interest, e.g, a gas mixture for a C02 laser) which receives a potential from power source 13', which may be different from the power source 13 which drives a plasma 6 in the sample cell 10. A sample can be inserted into the sample cell 10, via a fluidic system 9, from an analyte source 17. The pressure in, or the flow
through, the sample cell 10 is defined by a vacuum pump 18. The sample cell 10 and the active laser medium 16 are located between two reflectors 22 and 22' in the cavity 14 of the laser 15, where the first reflector 22 can be an output coupler and the second reflector 22' can be a grating. A shutter 19 connected to a modulator 20 chops the laser beam 7, creating a frequency dependent optogalvanic response in the sample cell 10, which is measured by a detector 12, connected to the power source 13. The measured signal is demodulated in a signal processing unit 21 triggered by the modulator 20, yielding the optogalvanic signal. For quantitative measurements, the sample cell 10 is illuminated by a second laser beam from a reference laser 15'. The reference laser 15' has a separate shutter 19', operating at a different frequency than the shutter 19 of the laser 15 with the laser medium 16. Two optogalvanic responses are measured by the detector 12, and demodulated by the signal processing unit 21 into two unambiguous optogalvanic signals
[0010] In ordinary OGS, the ionized sample is located in the laser beam path, i.e. outside the laser, whereas in ICOGS the sample is inserted into the laser cavity itself. In both cases, the analyzed carbon is in the form of C02. The intracavity approach has been suggested to increase the sensitivity by almost seven orders of magnitude compared with ordinary "extracavity" OGS. However, in many applications, the sensitivity of extracavity OGS is sufficient, and the plasma source can be kept outside the laser. A spectrometer for extracavity OGS of 13 C/ 12 C ratios is sometimes referred to as a laser-assisted ratio analyzer (LARA).
SUMMARY
[0011] Embodiments include a plasma source that includes a split-ring resonator having a first side and a second side, a first dielectric material having a first side facing the first side of the split-ring resonator and a second side opposite to the first side, a first electrically conductive ground plane facing the second side of the first dielectric material, a second dielectric material having a first side facing the second side of the split-ring resonator, and a second electrically conductive ground plane facing the second side of the second dielectric material.
[0012] Further embodiments include an optogalvanic spectroscopy system that includes a laser and a split ring resonator plasma source.
[0013] Further embodiments include an optogalvanic spectroscopy system that includes a laser, a detector, a split-ring resonator plasma source having a gap, at least one probe located in the gap of the split-ring resonator, a probe connection connecting the at least one probe to the detector, and a power source connection separate from the probe connection connecting the split-ring resonator to the power source.
[0014] Further embodiments include an optogalvanic spectroscopy method that includes generating a plasma in a gap of a split-ring resonator plasma source, such that an analyte is located in the plasma in the gap, providing laser radiation through the analyte located in the plasma in the gap, and detecting at least one electrical property of the plasma.
[0015] Further embodiments include a detection method that includes providing power from a power source through a power source connection to a split-ring resonator plasma source to generate a plasma in a gap of a ring of the split-ring resonator, and detecting at least one electrical property of the plasma in the gap using at least one probe connected to a detector using a probe connection separate from the power source connection.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate exemplary embodiments of the invention, and together with the general description given above and the detailed description given below, serve to explain the features of the invention.
[0017] Figures 1(a) to 1(c) illustrate a prior art microstrip split ring resonator (MSRR) plasma source, wherein Figure 1(a) is a side cross sectional view through a prior art MSSR plasma source, Figure 1(b) is an overhead view of a prior art MSRR plasma source, and Figure 1(c) is a side cross sectional view of part of a prior art MSRR plasma source with plasma in the gap.
[0018] Figure 2 is a schematic illustration of a prior art intracavity optogalvanic spectroscopy (ICOGS) system.
[0019] Figures 3(a) to 3(f) illustrate a stripline split ring resonator (SSRR) plasma source according to an embodiment, wherein Figures 3(a) to 3(c) illustrate side cross sectional views of
the SSRR plasma source and Figures 3(d) to 3(f) are top views showing the split-ring resonator containing part, a countersink containing part and the assembled device, respectively.
[0020] Figure 4 is a plot illustrating experimentally obtained shifts in resonance frequency due to the proximity of a metallic object to a microstrip and a stripline split-ring resonator, respectively.
[0021] Figure 5 is a side cross-sectional close-up view of a gap portion of a stripline split-ring resonator plasma source illustrating a cut through the source's gap and showing a geometry of the plasma in the split-ring resonator.
[0022] Figure 6 is a side cross-sectional close-up view of a gap portion of a stripline split-ring resonator illustrating a cut through the source's gap and illustrating a laser spectroscopy application.
[0023] Figure 7 is a side cross-sectional close-up view of a gap portion of a stripline split-ring resonator illustrating a cut through the source's gap and illustrates a sealed sample cell for an intracavity optogalvanic spectroscopy (ICOGC), cavity ring-down spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS) or off-axis integrated cavity output spectroscopy (OA-ICOS) application.
[0024] Figures 8(a) and 8(b) are top views of the central portions of a respective split-ring resonator containing part (Figure 8(a)) and a countersink containing part (Figure 8(b)) of a stripline split-ring resonator in a spectroscopy system according to an embodiment.
[0025] Figure 8(c) is a close-up view of the split-ring resonator of Figure 8(a) illustrating the position of probes with respect to a plasma in a hole.
[0026] Figure 9 is a schematic illustration of a ICOGS system containing a split-ring resonator with a separated signal detector and power supply.
[0027] Figure 10 is a schematic illustration of a CRDS, ICOS or OA-ICOS system containing a split-ring resonator with a separated signal detector and power supply.
[0028] Figure 11 is a calibration curve for an extracavity optogalvanic measurement employing a stripline split-ring resonator as a sample cell.
[0029] Figure 12 is a drawing of two embodiment plasma source devices without windows, illustrating the electric and fluidic connections.
DEAILED DESCRIPTION
[0030] The various embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes, and are not intended to limit the scope of the invention or the claims.
[0031] Various embodiments are directed to a miniaturized plasma source, and in particular a miniaturized split-ring resonator plasma source. Further embodiments include a laser spectroscopy system comprising a miniaturized plasma source, and laser spectroscopy methods using a miniaturized plasma source.
[0032] The inventors have discovered that although prior art microstrip split-ring resonators (MSRRs) possess a number of advantages as summarized above, they also suffer from some major disadvantages. From a miniaturization and integration point of view, the most severe limitation of MSRRs stems from their intrinsic design. An MSRR is designed with certain assumptions regarding the electric and dielectric environment surrounding it. Most often the microstrip is assumed to have the dielectric substrate and the ground plane beneath it and free space above. This opposes one of the most common motivations for miniaturizing a system, namely the enabling of high-level integration, in turn facilitating the construction of mobile or even handheld devices. An MSRR in an integrated system is not only sensitive to what other components are stacked on top of, or mounted close to, the dipole, but also to where the device is operated, since such variations will, to some extent, contradict the initial assumption regarding the dielectric environment. Although the effect of stationary parts could be accounted for, a device with integrated MSRRs would not be compatible with moving parts such as valves or pistons, since these would make the dielectric properties of the surroundings time dependent. Uncontrolled and random sources of noise would have the same effect. This sensitivity is of course particularly problematic for devices used in field hardware, for which the environment is unknown. For example, a device placed on a table would have different resonance characteristics
depending on if it is placed close to or far from, e.g., a metallic leg. Hence, MSRRs have major electromagnetic compatibility (EMC) issues.
[0033] The inventors have also discovered that another disadvantage of MSRRs is the geometry of the generated plasma. As explained above, the electrical field generating the plasma is concentrated in the plane between the ends of the dipole. Hence, the plasma will have the dielectric substrate on one side and free space on the other. This close proximity to the dielectric can be a major disadvantage in spectroscopic applications where substances or elements present also in the substrate material may be studied, since the plasma may cause erosion of the substrate, thus contaminating the sample and/or plasma and causing an erroneous analysis. Moreover, the MSRR only facilitates emission spectroscopy, where the direct emissions in the plasma are studied, but not the many kinds of laser spectroscopy, where laser light interacts with the plasma.
[0034] The inventors have also discovered that new applications of OGS, along with rising demands from the traditional clients, have created an increasing demand for more sensitive and less expensive measurement methods, and, even more important, methods that suffice with smaller samples. ICOGS can handle samples in the sub-microgram range. The limiting factor is the amount of carbon that is required to fill the plasma chamber in which the sample is ionized, to an adequate pressure. This chamber is typically a hermetically sealed cavity equipped with a plasma source for ionizing the sample, and Brewster angle windows for reflection-free transmission of the laser beam through the cell. The diameter of the laser beam, the volume of the plasma, and pressure in the chamber have proven to be important parameters for the sensitivity. In order to minimize the sample size, it would be convenient to reduce the plasma volume so that less C02 is required to keep the cavity at a certain pressure. This would, in turn, require miniaturization of the plasma source.
[0035] The inventors have also discovered that a major disadvantage of current plasma cells in ICOGS spectrometers includes their relatively large volume (typically around 30 ml), their high cost (because they are typically custom made by a professional glass-blower), and the fact that they use the same circuitry to create the plasma and to measure the OG signal (making them more susceptible to voltage noise and thermal fluctuations).
[0036] One non-limiting objective of an embodiment of the present invention is to overcome the drawbacks of MSRRs, associated with system integration and EMC. This may be achieved by creating a stripline split-ring resonator, consisting of a split-ring resonator sandwiched between two dielectric substrates and two metal ground planes. In order to make the plasma accessible from the outside of the ground planes, a hole may be made through the gap between the ends of the split ring.
[0037] In one embodiment of a stripline split-ring resonator, the two ground planes act as an electromagnetic shield, protecting the split-ring resonator from electromagnetic interference due to changes in the electric or dielectric environment surrounding it. Hence, the two ground planes may greatly improve the EMC of the stripline split-ring resonator, which may virtually maintain its resonance regardless of whether it is integrated in a system with other electrical parts, and regardless of what kind of electromagnetic environment the system is operated in.
[0038] Another non-limiting objective of an embodiment of the present invention is to avoid chemical contamination of the plasma due to plasma erosion of the dielectric substrate. In a stripline split-ring resonator according to various embodiments, the electrical field, and consequently the plasma, may be concentrated in the plane between the ends of the split-ring resonator. Hence, the plasma may form in the hole though the gap of the split ring, and not be in close proximity to the dielectric. Hence, the risk of chemical contamination of the plasma due to plasma erosion of the dielectric substrate may be greatly reduced in the stripline split-ring resonator.
[0039] Another non-limiting objective of an embodiment of the present invention is to make split-ring resonators applicable to laser spectroscopy. This requires a laser beam to be directed through the plasma, uninterrupted by the dielectric or metallic parts of the device. In a stripline split-ring resonator according to various embodiments, this may be facilitated by making the hole through the gap sufficiently wide.
[0040] Another non-limiting objective of an embodiment of the present invention is to facilitate the use of a miniaturized plasma source in an intracavity optogalvanic spectroscopy (ICOGS) system to reduce the cell volume, cost and disturbances.
[0041] In order to minimize the cell volume, in various embodiments the hole through the gap of the stripline split-ring resonator may be made into a plasma cell by sealing it with two windows, transparent to the laser beam, and equipping it with a fluidic system for introduction of the sample. By doing so, the total volume of the cell may be reduced to around 10 μΐ as compared with 30 ml for an ordinary plasma cell in ICOGS, i.e., three orders of magnitude smaller.
[0042] In order to reduce cost, a stripline split-ring resonator according to various embodiments may be manufactured by means of microelectromechanical systems (MEMS) technology, which is used here in the widest sense including micromachining technology, microstructure technology, and microsystems technology. MEMS technology facilitates batch processing, which can greatly reduce the cost per part. Moreover, MEMS facilitates high-precision machining, including, e.g., laser ablation, micromilling, photolithography, physical and chemical vapour deposition, wire bonding, chemical wet and dry etching, and screen printing.
[0043] In order to further reduce the noise in the OG signal, the circuitry for creating the plasma in the stripline split-ring resonator, i.e., the RF power supply, may be separated from the circuitry for measuring the signal. This may be accomplished by providing two plasma probes in the hole of the stripline split-ring resonator and connecting them to the detector through separate conductors and connectors.
[0044] A miniaturized plasma source according to one embodiment of the invention is a stripline split-ring resonator plasma source 1 (alternately referred to herein as an "SSRR device" or "SSRR"), which may be made of two pieces as shown in Figures 3a-f. One piece 101 consists of a first dielectric material 3, with one side 111 of the dielectric material 3 containing a metal ground plane 2, and the other side 109 of the dielectric material 3 containing a split-ring resonator strip 2'. The split-ring resonator strip 2" comprises an electrically-conductive material, such as a metal or metal alloy. The other piece 103 consists of a second dielectric material 3 with one side 115 of the dielectric material 3 containing a metal ground plane 2 and the other side 113 of the dielectric material 3 having a countersink groove 4, in which the split- ring resonator strip 2' fits. When the pieces 101, 103 are put together (Figure 3c) they make up a stripline split-ring resonator plasma source 1. In order to make the plasma 6, which is formed in the gap 2A between the two ends of the split-ring, accessible to the outside dielectric
environment 3', a hole 5 may be made extending through the dielectric material 3 and the ground plane 2 in one or both of the pieces 101, 103, as illustrated in Figure 5.
[0045] Thus, as shown in Figure 3a, the "stripline" split-ring resonator 2' has a first (e.g., bottom) side 105 and a second (e.g., top) side 107. The split-ring resonator 2' comprises a split ring portion 201 having a gap 2A between the ends of the split-ring portion 201, as shown in Figure 3d. The split ring portion 201 generally has a circular shape when viewed from above, as shown in Figure 3d. The gap 2 A in the split ring portion 201 may be filled with an electrical insulator (i.e., dielectric material).
[0046] The first (e.g., lower) dielectric material 3 has a first (e.g., top) side 109 facing the first side 105 of the split-ring resonator 2' and a second (e.g., bottom) side 111 opposite to the first side 109, as shown in Figure 3a. Preferably, the first side 109 of the first dielectric material 3 contacts the first side of the split-ring resonator 2'. However, in other embodiments, additional layers or materials may be inserted between the first dielectric material 3 and the resonator 2'.
[0047] The first electrically conductive ground plane 2 faces the second (e.g., bottom) side 111 of the first (e.g., lower) dielectric material 3. Preferably, the second side 111 of the first dielectric material 3 contacts the first electrically conductive ground plane 2. However, in other embodiments, additional layers or materials may be inserted between them.
[0048] A second (upper) dielectric material 3 has a first (e.g., bottom) side 113 facing the second (e.g., upper) side 107 of the split-ring resonator 2' and a second (e.g., top) side 115 opposite to the first side 113. Preferably, the first side 113 of the second dielectric material 3 contacts the second side 107 of the split-ring resonator 2'. However, in other embodiments, additional layers or materials may be inserted between the second dielectric material 3 and the resonator 2'.
[0049] A second electrically conductive ground plane 2 faces the second (e.g., top) side 115 of the second dielectric material 3. Preferably, the second side 115 of the second dielectric material 3 contacts the second electrically conductive ground plane 2. However, in other embodiments, additional layers or materials may be inserted between them.
[0050] The first and the second dielectric materials 3 preferably comprise respective first and second electrically insulating plates (e.g., substrates). The first and second dielectric materials 3
may be made from the same or different electrically insulating materials. The first and the second electrically conductive ground planes 2 may each comprise a metal or metal alloy layer located on a second side 111, 115 of the respective first and second electrically insulating plates 3.
[0051] In the stripline split-ring resonator plasma source 1, the two ground planes act as an electromagnetic shield, protecting the split-ring resonator from electromagnetic interference due to changes in the electric or dielectric environment surrounding it. Hence, the two ground planes greatly improve the EMC of the stripline split-ring resonator, which may virtually maintain its resonance regardless of whether it is integrated in a system with other electrical parts, and regardless of what kind of electromagnetic environment the system is operated in. This can be seen in Figure 4, where a metallic object was positioned at different distances from a prior art MSRR (e.g., as shown in Figures l(a)-(c)) and a stripline split-ring resonator 1 according to the invention (e.g., as shown in Figures 3(a)-(f)), respectively. It is evident that the prior art MSRR suffered from considerable shifts in the resonance frequency due to the varying electromagnetic environment, whereas the stripline split-ring resonator 1 maintained its resonance frequency regardless of the position of the object. In an application, the frequency shift would make the MSSR more difficult to ignite and operate in a stable manner, whereas the stripline split-ring resonator 1 of the invention may maintain stable operation.
[0052] In one embodiment of the invention, the stripline split-ring resonator is used in a laser spectroscopy application Γ . In various embodiments of a laser spectroscopy system and method using a stripline split ring resonator 1, a laser beam 7 (e.g., laser radiation, such as UV, IR or visible light) may be directed through the hole 5 and the plasma 6, as illustrated in Figure 6.
[0053] As discussed above, laser spectroscopy techniques using a plasma source and an isotope- specific C02 laser, such as optogalvanic spectroscopy (OGS) techniques in general and intracavity optogalvanic spectroscopy (ICOGS) techniques in particular, have been shown to be effective for measuring the isotopic composition of carbon-containing samples. Highly sensitive measurements of isotope ratios have a wide range of applications, from medicine to archaeology. Most renowned are, perhaps, measurements of long-lived radioisotopes such as 14C, 10Be and 129I that can be used for, e.g., dating organic deposits in archaeology, and rocks and sediments in
geology. However, C measurements have also proven useful for isotopic labeling of drugs in clinical trials by microdosing, and for studying cell regeneration in the human body.
[0054] Replacing the C02 laser with a tunable semiconductor laser with selectable center wavelength, e.g., a quantum cascade laser, may enable detection of a wide variety of molecules, in addition to C02. For example, in the ICOGS system shown Figure 2, the active laser medium 16 may comprise a stack of semiconductor multiple quantum well heterostructures in the case of a quantum cascade laser. Examples of molecules that may be detected include different hydrocarbons and hydrogen, nitrogen and sulfur oxides, as well as more complex molecules such as explosives and drugs.
[0055] In addition to OGS and ICOGS, other spectroscopic detection schemes are possible. Examples of such techniques are cavity ring-down spectroscopy (CRDS) and integrated cavity output spectroscopy (ICOS). For the latter, off-axis integrated cavity output spectroscopy (OA- ICOS) is of particular interest. All these techniques utilize signal amplification in an optical cavity. Such a cavity consists of two highly reflective, parallel mirrors between which light is repeatedly reflected. The sample is then introduced into the cavity, making each pass of the photons add to the spectroscopic signal, which, hence, is greatly increased. The total
amplification is governed by the effective path length of the photons, i.e., the mean total distance they travel inside the cavity. The effective path length is, in turn, limited by the reflectance of the mirrors as well as by intracavity absorption not relating to the sample.
[0056] In all these methods (CRDS, ICOS and OA-ICOS), the detector - commonly a mercury- cadmium-telluride IR detector - may only be placed behind the cavity. Here, the signal is still enhanced, characterized by a greatly improved SNR, but has a very low strength. More precisely, the strength of the signal outside the cavity is about (l-R)/2 times less than inside (R being the reflectivity of the mirrors), and, with highly reflective mirrors, this difference reaches several orders of magnitude. The low signal strength puts strict requirements on the sensitivity, and, more importantly, the noise floor of the detector, which often has to be cooled by liquid nitrogen. Moreover, the signal has to be amplified by advanced low-noise amplifiers if the full signal enhancement of the intracavity arrangement is to be obtained.
[0057] In one embodiment of the invention, the stripline split-ring resonator is used in an optogalvanic spectroscopy (OGS) application 1". This could be any kind of OGS, and is preferably one or more of intracavity optogalvanic spectroscopy (ICOGS), laser-assisted radio analyzer (LARA), cavity ring-down spectroscopy (CRDS), integrated cavity output spectroscopy (ICOS) or off-axis integrated cavity output spectroscopy (OA-ICOS). As shown in Figure 7, one or two laser-transparent windows 8 and a fluidic system 9 (in one embodiment a fluidic channel) may be added to the stripline split-ring resonator source 1 for laser spectroscopy applications 1 ' . The hole 5 through the stripline split-ring resonator 1 may be delimited by the windows 8, and may provide a miniature sample cell 10 in which the OGS measurements may be conducted. A fluidic system 9 may be used to insert the sample in the cell 10. The optogalvanic signal may be measured as the reflected power from the stripline split-ring resonator. If only one laser- transparent window is employed, the sample cell may be sealed by a mirror, or a non-transparent material.
[0058] In some embodiments, one or more (e.g. two) plasma probes 11 may be added to the stripline split-ring resonator 1" as illustrated in Figure 8, in order to measure the optogalvanic signal. In particular, at least one plasma probe 11 may be configured to monitor an electrical property of the plasma, such as plasma potential and/or impedance, or any other relevant electrical property of the plasma. The use of plasma, or Langmuir, probes 11 may be preferable since this enables more precise and accurate characterization of the plasma impedance, which is typically the measured entity in OGS, and can be used for spectroscopic signal detection in ICOGS, LARA, CRDS, ICOS and OA-ICOS.
[0059] Moreover, the use of plasma probes 11 allows for separation of the detector 12 and power supply 13 of the stripline split-ring resonator 1 " , which is advantageous from a signal-to-noise ratio point of view, since it removes the noise of the power amplifier from the measured signal. The probes 11 may comprise electrically conductive (e.g., metal or metal alloy) leads which are extended into the plasma 6 (see Figure 8c). The probes 11 may be contacted to two plasma probe pads 2". One of these probe pads 2" may be connected to one of the ground planes 2 of the stripline split-ring resonator 1", and the other probe pad 2" may be connected to the
optogalvanic signal detector 12 via a probe connection 23, such as an inner conductor of a coaxial cable, as shown in Figures 8(a) and 12. The shield of the coaxial cable may be connected
to the same ground plane 2 as the first plasma probe pad 2", or to the probe pad 2" directly. In contrast, a power source connection 24 (e.g., a coaxial power cable or another electrical connector) separate from the probe connection 23 may connect the split-ring resonator to the power source 13, as shown in Figures 8a, 9 and 12.
[0060] In an ICOGS application, as shown in Figure 9, the stripline split-ring resonator 1" may comprise a sample cell 10 inserted into the laser cavity 14 of a laser 15, with a lasing frequency corresponding to a transition in the spectrum of the laser medium 16 (which may be a moiety of interest, e.g., gas mixture, for a C02 laser, or a stack of semiconductor multiple quantum well heterostructures in the case of a quantum cascade laser), which is driven by a power source 13' , which may be different from the power source 13 which drives a plasma in the stripline split-ring resonator 1 ". A sample may be inserted into the sample cell 10, via a fluidic system 9, from an analyte source 17. The pressure in, or the flow through, the sample cell 10 may be defined by a vacuum pump 18. In this embodiment, the sample cell 10 and the active laser medium 16 are located between two reflectors 22, 22' in the cavity 14 of the laser 15, where the first reflector 22 can be an output coupler and the second reflector 22' can be a grating. A shutter 19 connected to a modulator 20 chops the laser beam 7, creating a frequency dependent optogalvanic response in the stripline split-ring resonator 1", which is measured by a detector 12. The measured signal is demodulated in a signal processing unit 21 triggered by the modulator 20, yielding the optogalvanic signal. For quantitative measurements, the sample cell 10 is illuminated by a second laser beam from a reference laser 15'. The reference laser 15' has a separate shutter 19', operating at a different frequency than the shutter 19 of the laser 15. Two optogalvanic responses are now measured by the detector 12, and demodulated by the signal processing unit 21 into two unambiguous optogalvanic signals. This ICOGS setup is unique in that the sample cell 10 is a stripline split-ring resonator 1", and that the power supply 13 is separated from the detector 12. In extracavity optogalvanic spectroscopy, e.g., LARA, the stripline split-ring resonator 1" constituting the sample cell 10 may instead be located outside the laser 15 in the path of the laser beam 7, so that the beam passes through the hole 5.
[0061] Figure 10 schematically illustrates an CRDS, ICOS or OA-ICOS application. In this embodiment, the stripline split-ring resonator 1" constitutes a sample cell 10 inserted into an optical cavity 25 consisting of two parallel reflectors 22" and 22"', which can be highly
reflective mirrors. Light from a laser 15 with a lasing frequency corresponding to a transition in the spectrum of laser medium 16 (which may be a moiety of interest, e.g., gas mixture, for a C02 laser, or a stack of semiconductor multiple quantum well heterostructures in the case of a quantum cascade laser) is directed into the optical cavity 25, and reflected back and forth between the cavity reflectors 22" and 22"'. A sample can be inserted into the sample cell 10, via a fluidic system 9, from an analyte source 17. The pressure in, or the flow through, the sample cell 10 may be defined by a vacuum pump 18. The sample cell 10 is located between the two mirrors 22" and 22"' in the optical cavity 25 separate from the laser 15. A shutter 19 connected to a modulator 20 chops the laser beam 7, creating a frequency dependent optogalvanic response in the stripline split-ring resonator 1 ", which is measured by a detector 12. The measured signal is demodulated in a signal processing unit 21 triggered by the modulator 20, yielding the optogalvanic signal. For quantitative measurements or measurements of more than one molecular species, the sample cell 10 may be illuminated by additional laser beams from one or more reference lasers 15'. Each reference laser 15' may have a separate shutter 19', operating at a different frequency than the shutter 19 of the laser 15. Two optogalvanic responses are now measured by the detector 12, and demodulated by the signal processing unit 21 into two unambiguous optogalvanic signals. CRDS, ICOS or OA-ICOS may also utilize plasma probes 11 which allows for the separation of the power supply 13 from the detector 12.
[0062] An advantage of the optogalvanic sensor using a stripline split-ring resonator according to various embodiments is its transparency to the incident radiation (e.g., laser) beam.
Conventional absorption spectroscopy sensors measure the signal by collecting photons. Hence, placing such a sensor inside an optical cavity would block the beam-path, and remove any intracavity enhancement effects. The sensor of the present invention, on the other hand, does not absorb photons apart from those that interact with the sample gas. Instead, it measures the effect of such interactions on the impedance of the plasma. Hence, the sensor can be placed inside the cavity without blocking the beam. Inside the cavity, the signal enhancement may be
characterized by increased signal strength instead of improved SNR. In other words,
embodiments of the present invention may enable access to the amplification as increased signal, instead of reduced noise, which is much easier to measure, and, consequently, the cavity enhancement can be utilized without the need for cryogenic cooling and complicated signal amplification. This in turn may enable the creation of a less complicated and expensive
spectroscopic platform, with applications in, for example, diagnostic medicine, greenhouse gas monitoring, gas alarms, detection of explosives or drugs, industrial process monitoring, etc.
[0063] Figure 11 shows results from extracavity OGS with a stripline split-ring resonator sample cell. Figure 12 depicts two such stripline split-ring resonator sample cells with the windows 8 removed and illustrating the electric 23, 24 and fluidic 9 connections, with the parts
corresponding to the device of Figure 8.
[0064] The miniaturized plasma source according to the embodiments of the invention can be made of a number of materials. The dielectric materials 3 may be, for example, a polymer, glass, ceramic, glass ceramic, combinations thereof, etc. For example, the dielectric may be printed circuit board (e.g., polymer), zirconium oxide, hafnium oxide or silicon, and may preferably be aluminum oxide, or fiberglass-reinforced hydrocarbon ceramic laminate. The electrically conductive material for the ground plane may be a metal or a metal alloy, e.g., platinum, silver, nickel or aluminum, and may preferably be copper or gold. The windows may be made of a material that is transparent to the radiation beam, such as diamond, silicon, or silicon dioxide, and may preferably be zinc selenide or germanium. The plasma probes and the connections may be made of any electrically conductive material, such as a metal or metal alloy, e.g., copper or aluminum, and preferably gold or platinum.
[0065] In various embodiments, the radius of the split-ring resonator 2' may be between 2.7 mm and 60 mm, to enable resonance between 0.5 GHz and 6 GHz for different materials, and may preferably be between 5.4 mm and 6.5 mm, which may enable resonance around 2.5 GHz, where a wide variety of electronics components is currently available. The width of the hole 5 through the gap 2A of the split-ring resonator, and the distance between the ends of the split ring, may be between 0.1 mm and 10 mm, to enable different kinds of fluidic and laser spectroscopy applications, and may preferably be between 1 mm and 5 mm, where the plasma is adequately simple to ignite in a pressure range typically being between 10 and 10000 Pa. The length of the plasma probes may be between 0.05 mm and 5 mm, and is preferably between 0.25 mm and 1.25 mm, i.e., 25% of the preferred width of the hole. The plasma probes 2" may be made of any kind of conducting wire which may have a radius of less than 0.05 mm to enable the wire to be wedged between the stripline split-ring resonator 2" and the adjacent dielectric material 3. The
plasma probes 2" may preferably be bond wires compatible with standard MEMS wire bonding. The windows 8 may be coated with an antireflective coating and may preferably be mounted at the Brewster angle of the laser beam.
[0066] The split ring resonator plasma source of the various embodiments may be fabricated in a number of ways. For example, the plasma source may be fabricated by joining of two essentially flat but structured or patterned members, and could also be successively formed by adding layers (structured or not) in a bottom up approach, or cast, or built up voxel by voxel, or by a combination of any of these methods. From this follows, e.g., that: "sandwiched" does not necessarily mean clamping, or even assembled in place, the embedment can be achieved, for example, by molding. Moreover, for the benefit of integration with other components, the split ring resonator plasma source may have a generally flat shape, such as shown in Figure 12, although it will be understood that the overall shape of the device need not be flat. Various embodiments of the split ring resonator plasma source could equally well be of a low aspect ratio (almost spherical or cubic) or, the opposite, of high aspect ratio (for instance tubular).
[0067] Apart from those mentioned above, the stripline split-ring resonator 1 could be used in a number of applications. In fact, any application requiring a substance to be transported from one volume into another, while going through some kind of ionization process would benefit from the invention, since it could be used as an ionizing aperture or orifice. Examples of such applications are chemical analysis, sterilization, and activation of substances.
[0068] The foregoing description of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The description was chosen in order to explain the principles of the invention and its practical application. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents.
[0069] Parts List
1. SSRR . SSRR in laser spectroscopy 1 ". SSRR in lCOGS
2. Ground plane 2'. Split-ring resonator 2". Plasma probe pads 201. Split-ring portion 2A. Gap in split-ring portion
ielectric Material 3' surrounding dielectric env.
ountersink
ole
lasma
aser beam
indow
luidic system
Sample cell
Plasma probes
Detector
Power source 13' Laser power source
Laser cavity
Laser 15' Reference laser
Laser medium
Analyte source
Vacuum
Shutter 19'. Reference shutter
Modulator
Signal processing
Reflector 22'. Reflector. 22' ' Reflector. 22' ' ' Reflector Probe connection
Power source connection
Optical cavity
. First piece of SSRR
. Second piece of SSRR
. First side of split-ring resonator
. Second side of split-ring resonator
. First side of first dielectric material
. Second side of first dielectric material
. First side of second dielectric material
. Second side of second dielectric material